Methods of making lignocellulose products and products resulting therefrom



United States Patent 3,241,991 METHODS OF MAKING LIGNOCELLULOSE PRODUCTS AND PRODUCTS RESULTING THEREFROM William T. Glab, Duhuque, Iowa, assignor, by mesne assignments, to Caradco Incorporated, a corporation of Iowa No Drawing. Original application Oct. 22, 1958, Ser. No. 768,832, now Patent No. 3,033,695, dated May 8, 1962. Divided and this application Nov. 13, 1961, Ser. No. 152,050

5 Claims. (Cl. 106-463) This invention relates to methods of making lignocellulose products and to the products resulting therefrom.

This application is a division of my copending application Serial No. 768,832, filed October 22, 1958, now Patent 3,033,695, issued May 8, 1962.

One of the objects of this invention is to provide an improved method of making a lignocellulose product capable of being pressure molded by reacting lignocellulose with a phenol in a confined atmosphere such as in an autoclave while supplying steam to this confined atmosphere during the reacting.

A further object of the invention is to provide products prepared by the above method.

Other objects and advantages of the invention will be apparent from the following description of several embodiments of the invention.

An important advantage of the invention appears to be caused by controlling the reaction so that the alpha cellulose of the lignocellulose is reduced in molecular size sutficiently to prevent substantial swelling of subsequently fabricated products but not to the extent that toughness of fibre is lost. This latter occurs under drastic degradation and starts to become quite serious when approximately 25% of the lignocellulose has been lost as either gaseous or soluble by-products.

Another advantage appears to be the plasticization of the lignin component during the controlled cellulose degradation so that the lignin can subsequently be made to flow and function as a binder between the comminuted lignocellulose particles.

Another advantage is the provision of a relatively dry system so that high capacity for the processing of, for example, wood waste is attained. This is not possible in a wet process such as ordinarily found in a pulping process in which the reactor is charged with approximately 90% water which takes up space as well as requires the addition of large amounts of energy to bring the reaction medium to the proper temperature.

Another advantage is the contacting of lignocellulose or dry mixes of lignocellulose and other ingredients under superatmospheric pressure with a vapor or combination of vapors functioning both as a heat transfer medium and as a reactant.

In the method of this invention an essentially dry mixture including comminuted lignocellulose and a phenol is reacted as by heating while confining the lignocellulose and the reactant under superatmospheric pressure as in an autoclave. During the reaction the lignocellulose bond is apparently broken and the lignin is released to operate as a binder.

It appears that the hemi-celluloses are the primary constituents of the lignocellulose which are attacked by hydrolysis, but that under the high pressure and temperature of this invention a portion of the hydrolysates are further converted to higher molecular weight material which can function as plasticizers for the autoclave prodnot when it is molded. At the same time a controlled degradation of the alpha cellulose is carried out to the extent that the desired degree of moisture stability is ob- 324L991 Patented Mar. 22, 1966 tained in the molded or extruded products without an unnecessary loss of toughness. The actions are believed to occur although they have not been absolutely proven.

The methods of this invention may be carried out batchwise in an autoclave or sealed press or continuously in a continuous contactor.

The essentially dry lignocellulose which appears dry to the touch actually contains up to about 30% water before the reaction begins.

The lignocellulose which may be used in this invention includes wood as Well as other lignocellulosic vegetable materials. The lignocellulose is finely divided so that the particles are preferably not more than 20 mesh in size as measured by a standard ASTM screen although smaller sizes are preferred.

During the reaction which takes place in a confined atmosphere under superatmospheric pressure various reaction products are produced, although the exact nature of the reaction is not understood. It appears that the reaction products are either inert so that the product itself is inert, have a binding action such as is true of the lignin produced, are gaseous by-products, or are polymerized. By hydrolyzing and partially removing, or polymerizing, the hemi-celluloses to lignin type materials, the ratio of lignin and other binders to the alpha cellulose is increased so that the general nature of the lignocellulose mixture is drastically changed.

The high pressure method of this invention has a number of advantages that are not possible with reactions taking place at ordinary pressures and in an unconfined state. In the preferred process, steam is introduced into the autoclave both for heating purposes and to supply moisture for the reaction. In the high pressure method of this invention heat transfer is much more rapid so that in general a shorter reaction time is required. Furthermore, energy losses during the reaction are greatly reduced. In the ordinary reacting mixture these energy losses result from the release of volatile materials such as water vapor, gaseous reaction by-products and the like. As the reaction here takes place in a confined atmosphere, no such losses occur to any material degree. Furthermore, the energy supplied by the steam or vapor is utilized to heat only the lignocellulose with its approximately normal moisture content in contrast to pulping type reactions where large quantities of water are present, requiring far greater expenditures of energy.

Another important advantage of this process is the close control that is obtained over the reaction. Thus the temperature of the reacting mass, and hence the rate of reaction, can be easily raised or lowered by controlling the rate of flow, pressure and the temperature of the heat transfer medium which may be steam, oil vapor, or other high temperature fluids. Reactions may easily be stopped by flashing the heat transfer medium from the autoclave since the large energy loss on expansion cools the reacting mass below the incipient reaction point. During the practice of the process the reacting mixture may be confined in a jacketed vessel with the heating medium introduced to the chambers in the quantity and temperature desired.

A very important advantage of the invention is that volatile reactants may be used as the reacting mass is in a confined space. Volatile reactants are impossible, of course, when the reacting mass is in the open. As a result of the rapid heat transfer achieved by this invention and the penetration of volatile reactants the reaction not only proceeds to completion in a much shorter time but the final product tends to be more uniform than where the reactants are heated such as in an ordinary process that depends upon surface temperature differentials.

Tests have shown that the confining of the reacting mass in the autoclave not only causes retention of the by-products of reaction within the mass even when the by-products are gaseous but also causes polymerization of all or a portion of these by-products, even some that are gaseous.

In so-called wet processes large quantities of the by-prod- 'ucts of reaction go into solution and are lost.

Another advantage of the invention is that the volatile hy-products are easily collected and removed at low cost for later use where desired or to prevent the creation of a nuisance.

Where volatile reactants are used no mechanical mixing of the ingredients is required. This results in a considerable saving in time, labor and other factors. Thus, in these instances, it is only necessary to charge the reactor with the lignocellulose and introduce the volatile materials into the reactor under superatmospheric pressure. In addition, if desired, the reactants can be changed or modified during the course of a run. This is not possible to such a degree in a wet process where the charge contains less than 50% of lignocellulose, and the addition of reactants would in many cases cause prohibitive amounts to go into solution.

A further advantage of utilizing the vapor process is that the volatile content of the reaction product which is primarily moisture can be controlled. By using superheated steam with a sufficient degree of superheat, products on the order of 1% or lower volatile content can be obtained. Under normal conditions, to degrees of superheat at 300 pounds per square inch steam pressure will produce a product of 3-5 volatile content. Thus the expensive drying step connected with wet processes can be avoided.

Because of rapid penetration of reactants under high pressure, larger sized particles can be charged to the autoclave than would ordinarily be used, and a savings in size reduction cost made as a result of lower power requirements to reduce the treated material in comparison with raw lignocellulose.

In addition, where flat stock of preformed material is being made as in a sealed press, the products can be made much thicker and more uniform than in an ordinary press which depends upon high platen temperature for heat transfer, and in many cases requires almost prohibitive cycle times.

The reactant is thoroughly mixed with the finely divided lignocellulose and then healed at a temperature and pressure and for a time sufiicient to react chemically at least a portion and preferably a major portion of the reactant or reactants with the lignocellulose.

In the peferred process the temperature of the steam is between about 275-475 F. and the pressure is between about 50-550 pounds per square inch gauge. The amount of reactant is preferably between about 0.130.0% by weight of the lignocellulose.

In the practice of this invention where solid reactants are used, they are preferably finely divided, and blended with the lignocellulose such as in a mixer, prior to the reaction in the autoclave. When liquids are used, they may be diluted with water or other solvents so that they will be thoroughly dispersed throughout the mass of lignocellulose. Preferably an amount of solution up to about 30% of the weight of the lignocellulose is utilized. If both solids and liquids are added, the solid is preferably blended with the lignocellose before the addition of the liquid.

EXAMPLE 1 To 500 grams of mesh, hammer-milled Ponderosa pine containing only its normal moisture content of approximately 6% was added grams of phenol. The mixture was ball-milled for one-half hour to obtain a uniform mixture. This composition was then placed in a heated autoclave and steam was admitted until the pressure was 400 pounds per square inch gauge and the temperature was approximately 460 F. The autoclave was held under these conditions for thirty minutes and then the steam was rapidly flashed off. During the course of the run, the pressure was maintained at about 400 pounds per square inch gauge by venting off the excess pressure caused by volatile reaction products. The granular reaction product which was cooled below the incipient reaction point by the rapid flash-off was removed from the autoclave and all particles which had consolidated were thoroughly broken up.

In substantially the same manner as specified in Example 1, reaction products were prepared under the tabulated conditions given in the following table. This table sets forth the quantity of reactant used based on the weight of the lignocellulose, the reaction time in the autoclave and the autoclave conditions that were maintained during each run.

Table Autoclave Reaction Example Reactant Time,

Min. Temp, Press.,

F. psi.

5% Phenol +1% Ferric 15 440 300 Chloride. 10 o Phenol +10% Sulfur-. 20 440 300 10 O Phenol +10% Sulfur 20 440 300 +10% Aniline. 5% Cresol 25 440 300 5% Cresol +31% Alnrnoni- 30 440 300 um Hydroxide. 5% Cresol +12% Calcium 30 460 400 Hydroxide. 5% Cresol +3% Calcium 20 440 300 Chloride. 5% Cresol +5 p.s.i. Sulfur 20 440 300 Dioxide. 5% Cresol +10% Sulfur 20 440 300 10% Cresol +10% Sulfur 20 440 300 +10% Ammonium I-Iydroxide. 5% Phenol Residue 20 440 300 10% Phenol Residue 30 460 400 5% Phenol Residue +05% 20 440 300 Ammonium Chloride. 5% Phenol Residue +3% 20 440 300 Calcium Chloride. 10% Phenol Residue +2% 15 440 300 Zinc Chloride. 10% Phenol Residue +5 20 440 300 p.s.i. Sulfur Dioxide. 18 5% Phenol Residue +3% 25 440 300 Paraformaldehyde +3% Tar Bases A. 19 10% Pentachlorophenol. 20 440 300 All of the percentages given herein are by we1ght of the lignocellulose.

The preferred range of the phenols is l25%.

Where bases are used in the high temperature, high pressure reaction, they appear to function as buffers to some extent. Thus, in general, somewhat higher pressures or longer reaction times are employed where they are used.

From the examples cited, it is apparent that a large number of different lignocellulose reactions can be carried out with the methods of this invention to produce materials having a wide variety of properties. Thus it it possible to produce reaction products which when molded or pressed or otherwise formed into products such as boards will possess an optimum of certain desired physical properties such as low water absorption, high strength, relatively high plasticity, or other required properties.

The materials thus formable at a relatively low temperature in the approximate range of 275-375 F. without use of excessive pressures. The temperatures at which the products are formed is not critical since boards can easily be made at about 400 F. or higher if desired. The ability to form products at lower temperatures is an important property since many of the synthetic resins formable at this temperature can thus be blended with the modified lignocellulose, if it is desired, to further vary the physical properties of the product.

Formed products can be produced over a wide density range such as with a specific gravity of from approximately 0.5-1.5 depending upon the temperature and pressure used. The pressure utilized can vary from about 255000 lp.s.i. depending upon the molding temperature and the product density required. In general, the lower pressures are used at the higher temperatures. Where boards or preforms are produced the temperature is generally between about 300-400" F. If the materials are molded the higher pressures are used the temperature preferably is between about 275-375 F.

Where boards or preforms are made the particle size of the composition of this invention is preferably between fit-inchl00 mesh as measured on standard screens. The especially preferred particle size is between 20-50 mesh. The press time is only sufficient to cause the particles to coalesce and bond to each other and to reach the desired board density. The time will, of course, vary with the applied pressure, press temperature and with the material used as well as the thickness of the board. In general the press time is between about 02-20 minutes. A Ai-inch thick board can ordinarily be made in 6-8 minutes at a temperature of 350 F. and under 100 p.s.i. pressure.

Where the reaction products of this invention are molded, the product is preferably removed from the reaction vessel and then ground to a powder that is preferably not over about 50 mesh in size. The finely divided moldable material is heated to a temperature just suffioient to how and fill the mold under the pressure used. The molding time is only sutficient to cause the moldable material to till the mold and set, and will vary depending upon the type of mold being used, the temperature, the nature of the moldable material and similar factors. In general, the molding time will vary between about 0.2- minutes.

Having described my invention as related to the embodiments set out herein, it is my intention that the invention be not limited by any of the details of description, unless otherwise specified, but rather be construed broadly within its spirit and scope as set out in the ac companying claims,

I claim:

1. The method of making a lignocellulose product capable of being pressure molded, consisting essentially of: intimately mixing finely divided l-ignocellulose material with O.130.0% by weight of phenol to provide a mixture; heating said mixture in a confined atmosphere at an internal pressure of about 550 pounds per square inch gauge and a temperature of about 275-475 F. for about 460 minutes to react said phenol and lignocellulos-e; and supplying steam to said confined atmosphere during the reacting whereby the lignocell ulose reacts simultaneously with said phenol and moisture from said steam in a hydr-olysis reaction.

2. The method of claim 1 wherein said reactant consists essentially of phenol.

3. The method of claim 1 wherein said reactant consists essentially of cresol.

*4. The unethod of claim .1 wherein said reactant consists essentially of pentachlorophenol.

5. A lignocellulose product prepared by the method of claim 1.

References Cited by the Examiner UNITED STATES PATENTS 2,036,156 3/1936 Lundback 18-475 2,130,783 9/1938 Sherrard et al. l847.5 2,156,160 4/1939 Olson 106-l63 2,291,433 7/1942 Hatch 1847.5

FOREIGN PATENTS 497,477 12/ 1938 Great Britain.

MORRIS LIEBMAN, Primary Examiner.

JOSEPH REBOLD, ALEXANDER H. BRODMERKEL,

' Examiners. 

1. THE METHOD OF MAKING A LIGNOCELLULOSE PRODUCT CAPABLE OF GEING PRESSURE MOLDED, CONSISTING ESSENTIALLY OF: INTIMATELY MIXING FINELY DIVIDED LIGNOCELLULOSE MATERIAL WITH 0.1-30.0% BY WEIGHT OF PHENOL TO PROVIDE A MIXTURE; HEATING SAID MIXTURE IN A CONFINED ATMOSPHERE AT AN INTERNAL PRESSURE OF ABOUT 50-550 POUNDS PER SQUARE INCH GAUGE AND A TEMPERATUREE OF ABOUT 275-475*F. FOR ABOUT 4-60 MINUTES TO REACT SAID PHENOL AND LIGNOCELLULOSE; AND SUPPLYING STEAM TO SAID CONFINED ATMOSPHERE DURING THE REACTING WHEREBY THE LIGNOCELLULOSE REACTS SIMULTANEOUSLY WITH SAID PHENOL AND MOISTURE FROM SAID STEAM IN A HYDROLYSIS REACTION. 